Substantive azo dyestuffs



l with halogen triazines with surprising ease and with good 2,963,473 Patented Dec. 6, 1960 United States PatentO ce wherein SUBSTANTIV E AZO DYESTUFFS Jakob Benz, Muenchenstein, and August Schweizer, Muttenz, Switzerland, assignors to Sandoz A.G., Basel', Switzerland, a Swiss firm N Drawing. Filed July 28, 1958, Ser. No. 751,120 Claims priority, application Switzerland Aug. 5, 1957 6 Claims. or. 260-153) R stands for a radical of the benzene series substituted with a sulfonic acid group or a carboxylic acid group or a carboxylic acid group plus a hydroxy group in ortho-position thereto,

A for the trivalent radical of a triazine compound in which the three halogen atoms originally linked to carbon atoms have been replaced by the two amine radicals B and C and the substituent z.

z for halogen or an amino group which may be monoor disubstituted,

One x for hydrogen or chlorine, and I The second x for hydrogen, fluorine, chlorine or bromine,

with the proviso that the two xs may not be two different halogens.

The production of green substantive dyestuffs by combining a yellow aminoazo dyestuif and a blue aminoanthraquinone dyestuff by means of a triazine compound containing two or three halogen atoms is known.

Of especial value are the substantive azo dyestuffs of the general formula (f NH:

son: l

The dyestuffs of this type which are manufactured on a technical scale have certain deficiencies which considerably limit their use in textile dyeing. The brightest members of this group of green direct dyestuffs, for example, are not sufficiently soluble for many purposes and are highly sensitive to salt, While other dyestuifs of the group having better solubility give appreciably duller shades than the first-named.

The employment for the production of green substantive dyestuffs of the above-mentioned type 'of yellow aminoazo dyestufis containing in the adjacent position to T P for productlqn P01131515 1n oolldenslPg the amino group an ionic water-soluble group is not de- 40 1 elther order One m 9 trlazme compound cfmtalIb scribed in the 1iterature h reason f this may he mg three halogen atoms linked to carbon atoms with one that aminoazo dyestuffs which contain a sulfonic acid 1010f an amlnomolwazo wmpound 0f the formula wherein 30 s stands for a chlorine atom, an amino or a phenylamino group 1 stands for a hydrogen atom, a hydroxy or a sulfonic acid group, and

1: stands for a sulfonic acid group, when t denotes hydrogen, for a carboxylic acid group, when t denotes the hydroxy group, and for a hydrogen atom, when t denotes a sulfonic acid group.

group in adjacent position to the amino group, for ex- OOOH ample 4-amino-1.1'-azobenzene-3.4'-disulfonic acid, can be condensed with halogen triazines only with very poor R-N=N NH:

wherein R has the aforecited meaning, and with one yields or not at all. In view of this it would be expected that aminoazo dyestuifs with a carboxyl group in ortho position to the amino group would be similarly unamenmol of 1-amino-4-[4-(4"-amino-) -phenyll-phenyl-aminoable to condensation with halogen triazines. However, anthraquinone-2.3-disulfonic acid or with one mol of a it has been found that this is by no means the case, but derivative thereof substituted in the 6 and/or 7 positions that aminoazo dyestufis containing a carboxyl group in by halogen, and, if desired, in exchanging the third haloadjac ent position to the amino group can be condensed gen atom of the triazine ring in the resultant condensation product for the hydroxyl group or an amino group which may be monoor disubstituted.

Examples of suitable radicals R are 4-hydroxy-3-carboxyphenyl, 3-hydroxy-4-carboxyphenyl and 3- or 4-sulfophenyl.

The 1-aminoanthraquinone-2-sulfonic acids of formula B-H are obtained by condensation of the corresponding 1-amino-4-halogen-anthraquinone-Z-sulfonic acids, e.g. 1-

yields. In conjunction with suitable aminoanthraquinone dyestuffs brilliant green direct dyestuifs can be obtained which are superior'to the known bright green substantive dyestuffs in solubility and compatibility with salt while being at least equal to them in brilliancy and purity of shade. r

The present invention accordingly relates to substantive azo dyestuifs of the general formula amino-4-bromoanthraquinoneZ-sulfonic acid, l-amino- SOaH 4.-dibromoanthraquinone-Z-su1fonic acid, 1-amino'4- brorno-6- or -7-chloroanthraquinone-Z-sulfonic acid, 1- amino 4 bromo 6.7 dichloroanthraquinone 2 sulfonic acid and 1-amino-4-bromo-6-fluoroanthraquinone- 2-sulfonic acid with 4.4'-diamino-1.1'-diphenyl-3-sulfonic acid.

Illustrative of the triazine compounds having three exchangeable halogen atoms linked to carbon atoms which are suitable for the production of the new azo dyestutfs of this invention are cyanuric chloride and cyanuric bromide.

The condensation of amines with triazine compounds containing mobile halogen atoms is known. It is further known that the production of the primary condensation product, i.e. the replacement of the first halogen atom by the radical of an amine, proceeds without difficulty. For this reason temperatures around C. are chosen for the operation. The replacement of the second halogen atom by the radical of an amine requires a slightly higher temperature, for example 30 to 60 C. while replacement of the third halogen atom can only be accomplished at higher temperatures, e.g. 80 to 100 C., and with a readily reactive amine. Examples of amines of the required reactivity are aminobenzene, aminobenzenesulfonic acids, aminobenzenecarboxylic acids, 1 amino-4-acetylaminobenzene, N-methylaminobenzene, methylamine, dimethylamine, ethylamine, diethylamine, monoand diethanolamine. can also be exchanged for the hydroxyl or the amino group or it can be left in the dyestuff molecule; in this last case the dyeing operation is so conducted that this third halogen atom is exchanged for the residue of cellulose, yielding a chemical combination between the substrate and the dyestufi. The new substantive azo dyestuffs possess good solubility in water and good compatibility with salt as well as good affinity for cotton and fibers of natural or regenerated cellulose. They migrate well and reserve cellulose acetate; the dyeings or printings on cotton are resistant to prolonged boiling and high temperatures. These dyestuffs are therefore outstandingly suitable for dyeing and printing the above-mentioned cellulosic fibers in green shades of good fastness to light, water, washing and perspiration.

Those dyestuifs which contain a metalliz'able grouping in the radical R can be aftercoppered on the fiber, whereby the dyeings are given substantially improved fastness to wet agencies.

In the following examples the parts and percentages are by weight and the temperatures in degrees centigrade.

EXAMPLE 1 A neutral to weakly alkaline solution of 30.1 parts of 4-amino-4'-hydroxy-1.1-azobenzene 3.3-dicarboxylic acid in 600 parts of water is added in the course of 1 hour to a dispersion of 18.4 parts of cyanuric chloride in 300 parts of icewater. The mass is stirred for a further hour at 03, during which time a dilute sodium carbonate solution is dropped in so that the condensa- This third halogen atom Subsequently, the primary condensation product formed is filtered off and added to a solution of 60.9 parts of sodium 1-amino-4- [4'- (4"-amino -phenyl] -phenylaminoanthraquinone-2.3-disulfonate in 800 parts of water. The mass is heated to 65 and stirred for 10 hours, a weakly acid reaction being maintained by gradual addition of a dilute sodium carbonate solution. After the addition of 18 parts of aminobenzene the reaction mass is heated at for 2 hours. The ternary condensation product now formed is salted out, filtered otf and dried. The dyestuff is purified in the normal manner by redissolving and reprecipitating.

The yellow aminoazo dyestutf used here can be obtained by coupling diazotized 2-chloro-5-aminobenzene-1- carboxylic acid with Z-hydroxybenzene-l-carboxylic acid and subsequently exchanging the chlorine atom in the monoazo dyestuff formed for the amino group. The reaction with an aqueous ammonia solution is conducted preferably at temperatures above and if desired in the presence of catalysts such as copper salts.

The new dyestufi is a dark green powder which dyes cotton and regenerated cellulosic fibers from aqueous solution in bright green shades; on aftercoppering the shades become faster to washing and yellower.

The same green azo dyestuff is obtained when the anthraquinone derivative is first reacted with cyanuric chloride, and then the aminoazo compound and finally the aminobenzene.

The dyeing method is as follows.

0.2 part of the dyestufi obtained according to the above example is dissolved in 300 parts of lime-free water. 10 parts of wetted cotton fabric are entered in the bath at 30 and the temperature increased to 100 in 30 minutes and maintained at this point for 15 minutes. During dyeing 3-4 parts of sodium sulfate, dissolved 1:10 in water, are added in portions. After dyeing the cotton is left in the bath for 15-20 minutes to cool to 50 and then removed, rinsed with water, squeezed out and dried. The dyed cotton is aftertreated with copper sulfate or, preferably, with a basic cationic copper complex compound (obtainable according to Swiss Patents 253,709 and 261,048-52) which gives greatly improved fastness properties, especially to washing.

EXAMPLE 2 7 When the 30.1 parts of 4-amino-4-hydroxy-1.1-azobenzene-3.3'-dicarboxylic acid in Example 1 are replaced by 32.1 parts of 4-amino-3-carboxy-1.1'-azobenzene-3'- or -4'-sulfonic acid, a green substantive dyestuff is obtained giving attractive green shades on cotton which have good light and washing fastness but cannot be aftercoppered.

In the following table are listed examples of further dyestuffs having the general Formula I, which can be produced according to the method detailed in Example 1. Cyanuric chloride is the halogen triazine used in all these examples.

The examples are characterized in columns B-H and CH by the basic substances of the substituents B and C of general Formula I, by the substituent z in column z tion product gives a constant weakly acid reaction. 60 and by the shade of the dyeings on cotton.

Table Ex. B-H CH z Shade on No. Cotton 3 1 amino 6 chloro 4 [4' (4" amino) phenyl] -phe- 4 amino 4' hydroxy 1.1 azobenzene Phenylamlno Green.

nyl-aminoanthra-quinonc 2.3-disulfonic acid. 3.3-d1carboxylic acid. 4 1 amino 7 chloro 4 [4' (4 amino) phenyl] -...-do 3-carboxy-phenylamino Do.

phenyl aminoanthraquinone 2.3" disulfonie acid. 5 1 -amino 6.7 dichloro -4 [4 (4 -amino) -phenyl1- do... 4-sulfophenyiamlno.. D0.

phenylaminoanthraquinone 2.3 disulfonic acid. 6 1 amino 6 bromo 4 [4 (4" amino) phenyl] 4 ammo 3 carboxy 1.1 azobenzene 3-su1tophenylamino Do,

phenyl aminoanthraquinone 2.3 disulionic acid. 4'-su lionic acid. v V 7-.- 1 amino 6(7) fiuoro 4 [4 (4" amino) phenyl] 4 amino 3 earboxy 1.1 azobenzene Z-hydroxyethylamino Do.

phenylamino anthraqulnone 2.3 disulfonic acid 3-sulfonic acid. (Technical Mixture). 8 1 amino 4 [4 (4 amino) phenyl] phenylami 4 ammo 4 hydrox} 1.1 azobenzene Chlorine Do,

noanthraquinone- 2.3"-disu1iom'c acid. 3.3- dicarboxylic acid. 9 do 4 amino 3 hydroxy 1.1 azobenzene do.. Do.

3.4-dicarboxy1ic acid.

7 8 Having thus disclosed the invention What we claimif H the positions 6 and 7 by a halogen atom and a nucleus 1. A substantive azo dyestuff of the formula substituted in both positions 6 and 7 by chlorine atoms,

(ll) NH:

S0311 z A t I .7 1 1 N J) NH NH-O l-NH N=N--R N i SOQH 00H 15 z represents a member selected from the group consisting wherein of a chlorine atom, an amino group, a lower alkyl- R represents a radical selected from the group consisting ammo group a l9wer hydmxytlkylamm" group a of 3-sulfophenyl, 4-sulfophenyl, 2-carboxyphenyl, 4- (loyver a1ky1)'amm a dl'uower hydroxyalkyl) carboxyphenyl, 3-hydroxy-4-carboxyphenyl and 3-caramino group a phenylammo a carboxyphenyl' boxy 4 hydroxyphenyl 20 amino group, a sulfophenylammo group and a N-lower A is a nucleus selected from the group consisting of the alkyl'N'phenylammo group unsubstituted nucleus, a nucleus substituted in one of 2. The substantive azo dyestuff of the formula SOxH IZH H O NH NH-O (ii-NH N=N S 0 3H OaH C O OH O O OH 3. The substantive azo dyestufi of the formula (f NH,

soui m NE NH-C c-NH =N-S0tH N SOaH OOH 4. The substantive azo dyestufi of the formula 0 NH, II

I c 0 NH NH-C 21-NH N=N a SOaH OOH 80:15!

5. The substantive azo dyestuif of the formula menu: 1 a n N 6'. The substantive azo dyestufi of the formula S0311 EH,

References Cited in the file of this patent UNITED STATES PATENTS 2,167,804 Gubler et a1 Aug. 1, 1939 2,391,164 Kaiser Dec. 18, 1945 FOREIGN PATENTS 466,886 Great Britain June 4, 1937 UNITED STATES PATENT OFFICE CERTIFICATIGN OF CORRECTION Patent No. 2,963,473 December 6, 1960 Jakob Benz et al.

It is h'ereby certified that error appears in the above numbered petent requiring correction and that the said Letters Patent should readas corrected below.

Column 8, claim 2, for the right-hand portion of the formula reading :N 50 a IN 0H read COOH COOH Signed and sealed this 6th day of June 1961.. [SEA L) fittest:

EBNEST w. SWIDER DAVID L LADD Aiitesting Officer Commissioner of Patents 

1. A SUBSTANTIVE AZO DYESTUFF OF THE FORMULA 